Determination of Tetrafluoroborate, Perchlorate, and Hexafluorophosphate in a Simulated Electrolyte Sample from Lithium Ion Battery Production Thunyarat Phesatcha, Suparerk Tukkeeree, Jeff Rohrer 2 Thermo Fisher Scientific, Bangkok, Thailand; 2 Thermo Fisher Scientific, Sunnyvale, CA, USA Application Note 258 Introduction Lithium ion batteries are commonly used in portable consumer electronic devices. The electrolyte solution in these batteries consists of a lithium salt in an organic solvent. Commonly used salts are lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium hexafluorosilicate (LiSiF 6 ), and lithium tetraphenylborate (LiB(C 6 H 5 ) 4 ). Some organic solvents used in the electrolyte solution are ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, methyl formate, methyl acrylate, methyl butylate, and ethyl acetate. The electrolyte in lithium batteries may have a mixture of these lithium salts and organic solvents. The electrolyte s concentration in the solvent ranges from 0. to 2 mol/l, with an optimal range of 0.8.2 mol/l. The anions of the added lithium salts can be determined by ion chromatography (IC) to ensure that the solutions have been prepared at the proper concentrations. Here, the authors prepare simulated samples that contain either lithium tetrafluoroborate, lithium perchlorate, or lithium hexafluorophosphate in an equal mixture of ethylene carbonate, diethyl carbonate, and propylene carbonate, and demonstrate that the anionic content can be determined accurately using a Reagent-Free IC (RFIC ) system. The RFIC system allows the analyst to avoid the problems encountered in eluent preparation. The RFIC system also delivers excellent retention time reproducibility for easy and reproducible quantification in the analysis of lithium ion battery electrolyte solutions. Equipment Thermo Scientific Dionex ICS-000* system: DP Dual Pump DC Detector/Chromatography module with dual-temperature zone equipped with 6-port valve EG Eluent Generator module Thermo Scientific Dionex Chromeleon Chromatography Data System software Version 6.80 SR7 *This application can be conducted with any Dionex RFIC system. Reagents and Standards Deionized water (DI), Type I reagent grade, 8 MΩ-cm resistivity or better Lithium tetrafluoroborate (LiBF 4 Lithium perchlorate (LiClO 4 Lithium hexafluorophosphate (LiPF 6 Ethylene carbonate, 98% (C H 4 Diethyl carbonate, 99% (C 5 H 0 Propylene carbonate (C 4 H 6 Chromatographic Conditions Columns: Thermo Scientific Dionex IonPac AS20, 4 250 mm (P/N 0648) Guard: Dionex IonPac AG20, 4 50 mm (P/N 0654) Eluent Source: Thermo Scientific Dionex EluGen EGC II KOH Column (P/N 058900) with Thermo Scientific Dionex CR-ATC Continuously Regenerated Anion Trap Column (P/N 060477) Gradient Steps: Potassium hydroxide; 5 mm from 7 to 0 min 5 to 80 mm (Curve 4) from 0 to min and 80 mm from to 26 min Flow Rate:.2 ml/min Sample Volume: 0 µl Column Oven: 5 C Pressure: ~2200 psi Detection: Suppressed conductivity, Thermo Scientific Dionex ASRS 00 Anion Self-Regenerating Suppressor, 4 mm (P/N 060554) Thermo Scientific Dionex CRD 200 Carbonate Removal Device, 4 mm (P/N 06298), Recycle mode Suppressor Current: 28 ma
2 Preparation of Solutions and Reagents Stock Standard Solutions Dissolve 0.09, 0.2, and 0.05 g of lithium tetrafluoroborate, lithium perchlorate, and lithium hexafluorophosphate, respectively, in DI water in separate 00 ml volumetric flasks. Dilute to volume with DI water. Calibration Standard Solutions Prepare mixed calibration standard solutions by diluting a mixture of defined volumes of 000 mg/l stock standard solutions with DI water in a 0 ml volumetric flask. The volumes of each 000 mg/l stock standard solution and the prepared calibration standard concentrations are shown in Table. Table. Volumes of 000 mg/l stock standard solutions used to prepare calibration standards at the listed concentrations. of each Anion Volume of each 000 mg/l Stock Standard Solution (µl) Final Volume (ml) 5 50 0 0 00 0 20 200 0 Eluent The eluent generator (EG) produces the eluent using the Dionex EluGen EGC II KOH cartridge and DI water (8 MΩ-cm resistivity or better) supplied by the pump. The eluent concentration is controlled by the Chromeleon Chromatography Data System software. The Dionex EluGen cartridge requires at least 4 MPa (2000 psi) of system backpressure, which ensures optimal removal of electrolysis gas from the eluent produced by the generator. See the Dionex ICS-000 Operator s Manual (Document No. 0650-04) for instructions on adding backpressure. Mixture of Three Carbonate Solvents (::) Thoroughly mix 0 g each of ethylene carbonate, diethyl carbonate, and propylene carbonate. Simulated Electrolyte Sample To simulate samples from lithium ion batteries, prepare three samples. Two samples are M solutions of lithium tetrafluoroborate and lithium perchlorate prepared in the mixture of three carbonate solvents. The third sample is a M solution of lithium hexafluorophosphate prepared in DI water. Later, this sample will be diluted : with the mixture of three carbonate solvents. This preparation is necessary because lithium hexafluorophosphate does not dissolve in the mixture of three carbonate solvents. Table 2 shows details of the sample preparation for these three samples. Table 2. Preparation of simulated samples. Simulated Sample M lithium tetrafluoroborate M lithium perchlorate M lithium hexafluorophosphate Weight of Lithium Salt (g) 0.98.068 Solvent Mixture of three carbonate solvents Mixture of three carbonate solvents Sample Preparation Tetrafluoroborate and Perchlorate Sample Dilute M lithium tetrafluoroborate and lithium perchlorate solutions 0,000 times with DI water. Final Volume (ml) Hexafluorophosphate Sample Mix M lithium hexafluorophosphate with the mixture of three carbonate solvents in a : ratio. Dilute this solution 5,000 times with DI water. Results and Discussion Chromatography The analyte anions in this application perchlorate, tetrafluoroborate, and hexafluorophosphate are classified as polarizable anions. These anions tend to be strongly retained and have poor peak shapes with typical anion-exchange columns. With anion-exchange columns, analysts often include organic additives in the eluent (for example, p-cyanophenol) to improve the peak shapes of polarizable anions. This is undesirable because it increases eluent costs, eluent complexity, waste disposal costs, and decreases detection sensitivity. To address this problem, we designed the Dionex IonPac AS6 column and later, the IonPac AS20 column. These are high-capacity, hydroxideselective, anion-exchange columns designed for polarizable anions. The stationary phases in these columns allow easy elution of polarizable anions with good peak shapes while requiring no organic solvent in the eluent. The high capacity allows the determination of polarizable anions in the presence of high concentrations of other anions. 0 0.59 DI water 0
In the analysis presented here, the authors used the Dionex IonPac AS20 column because it has higher column capacity than the AS6 column (0 µeq/column compared to 60); however, the AS6 column can also be used with different hydroxide eluent concentrations. Because both columns can be used with hydroxide eluents, they can be paired with an eluent generator (EG). An EG, the key component of an RFIC system, produces error-free pure hydroxide eluent. This translates to highly reproducible analyte retention times for reproducible determination without the labor involved in manually preparing hydroxide eluents. Figure shows the separation of three mixed standard solutions (used for method calibration) of the three analytes of interest: perchlorate, tetrafluoroborate, and hexafluorophosphate. The three anions were well separated in about 25 min, with the first analyte, tetrafluoroborate, eluting at about min. The first 2 min of the separation were included to allow most common inorganic anions to elute so that they did not interfere with the determination of the three analytes. Tetrafluoroborate eluted between sulfate and phosphate, while perchlorate and hexafluorophosphate eluted after phosphate. Table shows the calibration information for each analyte. 0 Conductivity (µs) Column: Dionex IonPac AS20 Analytical, 4 250 mm Dionex IonPac AG20 Guard, 4 50 mm Eluent Source: Dionex EGC II KOH Eluent: Potassium hydroxide; 5 mm from 7 to 0 min, 5 to 80 mm (Curve 4) from 0 to min, and 80 mm from to 26 min Flow Rate:.2 ml/min Inj. Volume: 0 µl Temperature: 5 C Detection: Suppressed conductivity, Dionex ASRS 00 Anion Self-Regenerating Suppressor, 4 mm, Dionex CRD 200 Carbonate Removal Device, 4 mm, recycle mode Sample: Mixture of 5, 0, and 20 mg/l calibration standard Peaks:. Tetrafluoroborate 5, 0, and 20 mg/l 2. Perchlorate 5, 0, and 20. Hexafluorophosphate 5, 0, and 20 2 0 5 0 5 20 26 Minutes 2779 Figure. Overlay of chromatograms of the calibration standards. Table. s of calibration standards and the calibration results reported by the Chromeleon software. Analyte Result Level Level 2 Level % Coeff.Det. Offset (µs * min) Slope (µs * min)/mg/l Tetrafluoroborate 5 0 20 00.00 0.0485 0.0606 Perchlorate 5 0 20 99.99 0.0597 0.062 Hexafluorophosphate 5 0 20 99.9 0.0449 0.0296
4 Sample Analysis Here, three simulated lithium ion battery electrolyte samples were prepared. One molar solution each of lithium tetrafluoroborate and lithium perchlorate was prepared in a mixture of three carbonate solvents. One molar lithium hexafluorophosphate was prepared in DI water and then diluted : with the mixture of three carbonate solvents. The first two samples were diluted to 0,000 and the third sample was diluted :5,000 with DI water prior to analysis by IC. Figure 2 shows the chromatography of each of the three samples. The Dionex CRD 200 Carbonate Removal Device was used to eliminate any possible interference from sample carbonate. Short-term reproducibility was measured by making five injections of each sample. The data in Table 4 show good reproducibility for the amount measured in each sample. To judge accuracy, the authors compared measured concentration to the calculated concentration (Table 5) and found that the measured concentration was between 97.4, 04, and 09% of the calculated concentration for perchlorate, hexafluorphosphate, and tetrafluoroborate, respectively. As a second test of accuracy, the simulated samples were spiked with 2 mg/l of the same anion prior to dilution. The data in Table 5 also show good recoveries for each anion, suggesting method accuracy. Conclusion This application demonstrates an IC method that uses an RFIC system to easily assay the anions in the simulated lithium ion battery electrolyte samples. The results show that this method is both accurate and reproducible. 5.0 Conductivity (µs) C B A Column: Dionex IonPac AS20 Analytical, 4 250 mm Dionex IonPac AG20 Guard, 4 50 mm Eluent Source: Dionex EGC II KOH Eluent: Potassium hydroxide; 5 mm from 7 to 0 min 5 to 80 mm (Curve 4) from 0 to min and 80 mm from to 26 min Flow Rate:.2 ml/min Inj. Volume: 0 µl Temperature: 5 C Detection: Suppressed conductivity, Dionex ASRS 00 Anion Self-Regenerating Suppressor, 4 mm, Dionex CRD 200 Carbonate Removal Device, 4 mm, recycle mode Samples: (0,000 times dilution) A. Tetrafluoroborate B. Perchlorate C. Hexafluorophosphate Peaks:. Tetrafluoroborate 9.5 2. Perchlorate 9.69. Hexafluorophosphate 5. 2 0.5 0 5 0 5 20 26 Minutes 27720 Figure 2. Chromatograms of samples (0,000 times dilution). Table 4. Assay results for the samples and spiked samples. Amount Injection No. Tetrafluoroborate Perchlorate Hexafluorophosphate Sample Spiked Sample Sample Spiked Sample Sample Spiked Sample 9.57. 9.74.9 5. 6.7 2 9.45. 9.68.9 5. 6.8 9.58. 9.75.7 5. 6.7 4 9.55. 9.69.8 5. 6.8 5 9.48.2 9.57.8 5.2 6.8 Average 9.5. 9.69.8 5. 6.8 RSD 0.62 0.55 0.74 0.64 0.0 0.26
Table 5. Assay results for the samples and spiked samples. Ion Calculated after 0,000 Times Dilution Average Found Recovery (%) Spiked Average Found in Spiked Sample Recovery (%) Tetrafluoroborate 8.70 9.5 09 2. 88.5 Perchlorate 9.95 9.69 97.4 2.8 06 Hexafluorophosphate 4.5 5. 04 2 6.8 85.0 Application Note 258 www.thermofisher.com/dionex 206 Thermo Fisher Scientific Inc. All rights reserved. Sigma-Aldrich is a registered trademark of Sigma-Aldrich Co. LLC. All other trademarks are the property of Thermo Fisher Scientific Inc. and its subsidiaries. This information is presented as an example of the capabilities of Thermo Fisher Scientific Inc. products. It is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others. Specifications, terms and pricing are subject to change. Not all products are available in all countries. Please consult your local sales representative for details. Australia +6 9757 4486 Austria +4 50 4 0 Belgium +2 5 7 42 4 Brazil +55 7 540 China +852 2428 282 Denmark +45 70 2 62 60 France + 60 92 48 00 Germany +49 626 99 0 India +9 22 2764 275 Italy +9 02 5 62 267 Japan +8 6 6885 2 Korea +82 2 420 8600 Netherlands + 76 579 55 55 Singapore +65 6289 90 Sweden +46 8 47 80 Switzerland +4 62 205 9966 Taiwan +886 2 875 6655 UK/Ireland +44 442 2555 USA and Canada +847 295 7500 AN7099_E 08/6S